JPS62178243A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To permit a quick color developing process by incorporating an auxiliary developer into at least one layer of photographic constituting layers hardened by using specific compds. and combining a specific compd. with a red sensitive silver halide emulsion layer. CONSTITUTION:At least one layer of the photographic constituting layers contg. the auxiliary developer are hardened by using chlorotriazine compd. expressed by formula I and/or formula II and the compd. expressed by formula III is incorporated in combination with the red sensitive silver halide emulsion layer into at least one layer of the photographic constituting layers. R1, R3, R4 are a chlorine atom, hydroxy group, etc., R2 is a group synonymous with R1. Q, Q' and the combination group selected from -O-, -S-, -NH-. L is an alkylene group, etc., l, m are 0, 1. R5, R6 are -CN or -CFR'R'', R' and R'' are H atom, F atom, etc. R7, R8 are an aliphat. group, arom. group etc. The defect of the chlorotriazine film hardening agent which deteriorates the shelf life of the red sensitive emulsion layer is overcome in the above-mentioned manner and unnecessary coloration is prevented.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic light-sensitive material that can be subjected to rapid color development processing and has excellent whiteness and film properties. Regarding.

[Background of the Invention] A silver halide color photographic material, which is one of the representative silver halide photographic materials, has a support selected to be sensitive to blue light, green light, and red light. Three types of spectrally sensitized silver halide photographic emulsion layers are coated. For example, in color negative photosensitive materials,
Generally, from the side exposed to light, a blue-sensitive emulsion layer, a green-sensitive emulsion layer,
A red-sensitive emulsion layer is coated in this order, and a bleachable yellow filter layer is provided between the blue-sensitive emulsion layer and the green-sensitive emulsion layer to absorb blue light that passes through the blue-sensitive emulsion layer. ing. Furthermore, each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various special purposes. In addition, for example, in a light-sensitive material for color marking WMM, a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are generally coated in this order from the side to be exposed, and each layer has a special coating, similar to the light-sensitive material for color negatives. For this purpose, intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known that each of these emulsion layers may be provided in a different arrangement from the above, and each emulsion layer may be provided with a photosensitive layer consisting of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use emulsion layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method,
Typically, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanoacetyl magenta couplers and acylacetamides are used to form cyan, magenta and yellow dye images, respectively. or benzoylmethane type yellow couplers are used. These dye-forming couplers are contained in the light-sensitive color photographic emulsion layer or in the developer solution. The present invention relates to a silver halide color photographic light-sensitive material in which these couplers are preliminarily contained in an emulsion layer and rendered non-diffusive.

Incidentally, in recent years, there has been an increasing demand for speeding up color development for reasons such as shortening delivery times and improving productivity in laboratories. In addition, from the viewpoint of cost, low pollution, etc., there are demands for low replenishment of color developing solutions and removal of harmful chemicals. In any of the above cases, a technology for speeding up color development is required to achieve this goal.

For this reason, various studies have been conducted to speed up color development.

As one method, it is known to use a color development accelerator when developing an exposed silver halide photographic light-sensitive material using an aromatic primary amine color developing agent. For example, as such a color development accelerator,
U.S. Patent Nos. 2,950,970 and 2,515,147
No. 2,496,903, No. 4,038.075, No. 4.119.462, British Patent No. 1.430.99
No. 8, No. 1,455,413, JP-A-53-1583
No. 1, No. 55-62450, No. 55-62451,
No. 55-62452, No. 55-62453, No. 51
-12422%, Special Publication No. 51-12422, No. 55-
Compounds described in No. 497211 etc. were investigated, but
Most of these compounds have insufficient development accelerating effects;
Moreover, among these compounds, even those which exhibit a sufficient development accelerating effect often have the drawback of forming fog.

Furthermore, JP-A No. 56-64339 describes a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide photographic light-sensitive material, and JP-A No. 57-144
No. 547, No. 58-50532, No. 58-50533
No. 58-50534, No. 58-50535, and No. 58-50532 disclose that 1-arylpyrazolidones are added to a silver halide photographic light-sensitive material.
Processing within extremely short development times is disclosed.

In addition, various penetrants have been studied to promote the penetration of color developing agents into silver halide photosensitive materials, and among these, a method of accelerating color development by adding benzyl alcohol to a color developer is widely used. It is being

Further, a method has been proposed in which color development is promoted by increasing the processing temperature, or a method in which color development is promoted by increasing the PL-1m degree of the color developer.

On the other hand, in order to speed up color development, a method is also known in which a color developing agent is incorporated into a light-sensitive material in advance, as described in US Pat. No. 3,719.492, for example.

Furthermore, in order to inactivate the amine moiety of a color developing agent, there is a method of incorporating the color developing agent into a Schiff salt, for example, as disclosed in U.S. Pat. No. 3,342,559.
Research Disclosure, 1976 N 0.1
5159.

In the color development acceleration method described above, considering the color development acceleration effect and the influence on other photographic performance, there is a method of incorporating an auxiliary developer into the silver halide photographic light-sensitive material, and a method of incorporating the color development solution temperature or Methods such as increasing the pH have been found to be particularly useful.

However, even the above method still has some insufficiencies. That is, when the above method is applied to photosensitive materials for printing, such as color photographic paper, an undesirable increase in density is observed, especially in unexposed areas, such as white edges of prints or white scene areas. However, it has the disadvantage that it appears colored, which significantly deteriorates the quality, and an improvement has been strongly desired.

As a result of extensive research into improving the above-mentioned drawbacks, it was found that the above-mentioned drawbacks could be improved by using a chlorotriazine-based compound as a hardening agent. However, the above-mentioned chlorotriazine-based hardeners often have high diffusivity in the hydrophilic colloid layer, and even if added to the auxiliary developer-containing layer, they will diffuse to other photographic layers and have an adverse effect. I understand. In particular, it has been found that it deteriorates the storage stability of the red-sensitive emulsion layer over time.

It has been found that the above-mentioned drawbacks of the chlorotriazine hardener can be improved by using a combination of specific compounds in the red-sensitive emulsion layer, and the present invention has been completed. .

[Objective of the Invention] The object of the present invention is to provide a silver halide photographic light-sensitive material that has excellent rapid processing properties, does not cause unnecessary coloring even when rapid processing is performed, has excellent film properties, and has overall excellent photographic performance. It is provided by.

[Structure of the Invention] The object of the present invention is to provide a photograph comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a non-light-sensitive layer on a support. In the silver halide photographic light-sensitive material having constituent layers, at least one of the photographic constituent layers contains an auxiliary developer, and at least the photographic constituent layer containing the auxiliary developer has the following general formula [I] and / or hardened using a compound represented by [II]; This was achieved by using a silver halide photographic light-sensitive material.

General formula [I] R.

In the formula, R1 is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, -0M (M is a monovalent metal atom, -NR'R'' group (R' and Rrt are each a hydrogen atom, alkyl group, aryl group) or -NH
COR'' represents a group (R'' is a hydrogen atom, an alkyl group, or an aryl group), and R2 represents the same group as R1 above except for a chlorine atom.

General formula [II] In the formula, R3 and R,) are each a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group or an -OM group (M
represents a monovalent metal atom). Q and Q' each represent a linking group selected from -0-1-S-1-NH-, and L represents an alkylene group or an arylene group. ! and marks represent O or 1, respectively.

In the following margin general formula [III, R5 and R6 are respectively -CN or -CFR]
'R' represents R'J3 and Rn each represents a hydrogen atom, a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.

R7 and R8 each represent an aliphatic group, an aromatic group or a heterocyclic group.

[Specific structure of the invention] Hereinafter, the configuration of the present invention will be specifically explained.

First, the general formula [II or [I] used in the present invention
The compound represented by [I] will be explained in detail.

In general formulas [II and [II], examples of the alkyl group represented by R1 include alkyl groups having 1 to 3 carbon atoms, such as methyl group, ethyl group, and alkoxy group, such as methoxy group. , ethoxy group,
Further, examples of the alkylthio group include a methylthio group and an ethylthio group.

Further, M representing a 10M monovalent metal atom represented by R1 includes, for example, sodium, potassium, etc.
Further, the alkyl group represented by R' and RTL of the -NR'R'' group includes an alkyl group having 1 to 3 carbon atoms, such as a methyl group and an ethyl group, and the aryl group includes, for example, a phenyl group.

The alkyl group and aryl group represented by R″′ of the 1N HCOR″ group roughly represented by R1 are the above-mentioned R′
and a group having the same meaning as the alkyl group and aryl group represented by RII.

R2 is a group having the same meaning as R1 as described above. However, R
1 and R2 cannot be chlorine atoms at the same time.

Next, the groups represented by R3 and R4 are the same as the group represented by R1 above.

Further, the alkylene group represented by L includes an alkylene group having 1 to 3 carbon atoms, such as a methylene group and an ethylene group. Further, as an arylene group, for example, a phenylene group can be mentioned.

Next, typical specific examples of the hardeners according to the present invention represented by the general formulas [II and [II] will be described.

Below margin (+-1) (1-2)N
HC2H.

(It-1) (It-2) CI C1(l[-3) (I[-4) (i5) (n-6) (II-8) (II-9) The general formula according to the present invention [ In order to add the hardener represented by [I] or [II] to the silver halide emulsion layer or other constituent layers, it is dissolved in water or a water-miscible solvent (e.g. methanol, ethanol, etc.), It may be added to the coating solution for the layer. The addition method may be either a batch method or an in-line method. The timing of addition is not particularly limited, but it is preferably added immediately before coating.

These hardeners are used in an amount of 0.5 to io per 1 g of coated gelatin.
omo, preferably 2.0 to 50 mg.

Next, the following general formula [
The compound represented by I[[] (hereinafter referred to as the dye of the present invention) will be explained.

General formula [I[] In the formula, R5 and R6 are respectively -〇N or -CFR
'R'' and R' and RII each represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to A carbon atoms.

R7 and R8 each represent an aliphatic group, an aromatic group or a heterocyclic group.

In the above general formula [II[], R5 and R6 each represent -〇N or -〇FR'R'', and -〇F
Examples of the fluorinated alkyl group of R' or Rn represented by R'R'' include difluoromethyl group, trifluoromethyl group, 1゜1.2.2-tetra-fluoroethyl group, 1,1゜2 .2.3.3.4.4-octafluorobutyl group, 1.1.2.2.3.3-hexafluoropropyl group, and the like.

R7 and R8 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and among these, the aliphatic group includes an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a methyl group, a hexyl group, octyl group, dodecyl group, etc.) cycloalkyl group (eg, cyclohexyl group, etc.), alkenyl group (eg, butenyl group, etc.). Furthermore, typical aromatic groups include aryl groups such as phenyl and naphthyl groups. Furthermore, representative examples of the heterocyclic group include a benzthiazolyl group and a benzoxasilyl group.

The aliphatic group, aromatic group, and heterocyclic group represented by R7 and R8 further include a hydroxy group, an amino group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Alkoxy group (e.g. methoxy group, ethoxy group, etc.),
It may be substituted with a carboxy group, a carbamoyl group, a sulfo group, a sulfamoyl group, an aryl group (eg, phenyl group, 4-sulfophenyl group, etc.), an aryloxy group (eg, phenoxy group, 4-sulfophenoxy group, etc.), or the like. In addition, an aryl group is an alkyl group having 1 to 4 carbon atoms (
For example, it may be substituted with a methyl group, an ethyl group, etc.).

Further, examples in which the aryl group represented by R7 and R8 are substituted with a sulfo group include a 4-sulfophenyl group, 3-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-chloro-4- Sulfophenyl group, 4-chloro-3-sulfophenyl group, 2-chloro-5-sulfophenyl group, 2-methoxy-4-sulfophenyl group, 2
-Hydroxy-4-sulfophenyl group, 2,5-dichloro-1-4-sulfophenyl group, 2,6-dimethyl-4-
Sulfophenyl! , 2.5-disulfophenyl group, 3.
5-disulfophenyl group, 4-phenoxy-3-sulfophenyl group, 2-chloro-6-methyl-4-sulfophenyl group, 3-carboxy-2-hydroxy-5-sulfophenyl group, 3.6-disulfophenyl group Examples include -α-naphthyl group, 8-hydroxy-3,6-disulfo-α-naphthyl group, 5-hydroxy-7-sulfo-β-naphthyl group, and 6,8-disulfo-β-naphthyl group.

Further, examples in which the heterocyclic groups of R7 and R8 are substituted with a sulfo group include a 2-(6-sulfo)benzthiazolyl group, a 2-(6-sulfo)penzoxasilyl group, and the like.

The sulfo group may also be bonded to an aryl group via a divalent organic group, such as 4-(4-sulfophenoxy)phenyl group, 4-(2-sulfoethyl)phenyl group, 3-(sulfophenoxy)phenyl group, methylamine) phenyl group, 4-(
2-sulfoethoxy)phenyl group may be mentioned.

Of the above R5 and R6, preferably 10N group, CF
It is an a group. Further, among R7 and R8, an aromatic group is preferable, and a 4-sulfophenyl group and a 2,5-di-sulfophenyl group are particularly preferable.

Typical examples of the dye of the present invention represented by the general formula [II1] are shown below, but the dye of the present invention is not limited thereto.

The following margins are illustrative dyes N a (J 3 S
SO3N aS○,K
b Rico Mr. C
H.

The dye represented by the general formula [I] is represented by the following general formula []11
It can be synthesized by reacting the 3-cyano-5-pyrazolone compound represented by a] with a compound represented by the following general formula [I[[I]] in the presence of a base.

General formula [I[[a] General formula [Ib 1 In the following blank formula, R3 represents the same meaning as in the above general formula [II[], and G represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom) , bromine atom), -valent group, trifluoromethyl group, ethoxycarbonyl group, etc. X
is an anion (e.g. chloride, bromide, iodide, verchlorate, p-toluenesulfonate, methylsulfonate, ethylsulfonate, etc.)
, and l represents O or 1.

The bases to be present include pyridine, piperidine,
Triethylamine, triethanolamine, morpholine, ammonia, etc. are used.

Solvents for the compounds include alcohols (e.g., methanol, ethanol, etc.), ethylene glycol, ethylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl alcohol, etc.), acetonitrile, dimethyl sulfoxide, amides ( For example, dimethylformamide, dimethylacetamide, acetamide, etc.) are used.

The reaction is suitably carried out at a temperature from 0°C to the boiling point of the solvent used.
The 3-cyano-5-pyrazolone compound represented by [a] is
It is appropriate to use about twice the molar amount of the compound represented by the general formula [II[b].

Furthermore, the 3-cyano-5-pyrazolone compound represented by the general formula cma can be synthesized using the manufacturing method described in British Patent No. 585.780.

Examples of synthesis of the dye of the present invention are shown below.
I will explain in detail.

Synthesis Example 1 (Synthesis of Exemplary Dye (1)) 10.6 iJ of 1-(4'-sulfophenyl)-3-cyano-5-pyrazolone and 5.7 g of glutacondialdehyde cyanyl hydrochloride were mixed with 100 g of dimethyl formaldehyde.
Then, 6.19 g of triethylamine was added thereto, and the mixture was stirred at room temperature for 4 hours. Next, methanol 15 (
5.9 g of potassium acetate dissolved in hff was added and stirred. The precipitated dye crystals were collected by filtration, washed with acetone, then methanol, and dried to obtain 9.7 g of dye.

The aqueous solution of this dye had a λmax of 645r+m.

Furthermore, dyes 15 to 26 used in the silver halide photographic material of the present invention can be produced by conventional methods. For example, mono-
, tri, and pentermedine oxonol can be synthesized. 3-Trifluoromethylvilazolone is J
analof American Chemical
5ociety (Journal on American Chemical Society), Vol. 68, p. 426, it can be easily synthesized by condensing trifluoroacetoacetate and the necessary hydrazine derivative. The manufacturing method of representative compounds among these dyes is shown below.

Synthesis Example (Synthesis of Exemplary Dye (15)) 1-(4'-sulfophenyl)-3-trisulfomethyl-5 pyrazolone 6,17(] and] venter 1,3-diene-dimethachloroanyl hydrochloride 354 (1) was added to dimethyl formaldehyde 30112, and 4.05 g of triethylamine was added thereto, followed by stirring at 20 to 25°C for 3 hours.

Next, add 7t12 of a 30% potassium acetate aqueous solution and add wood vinegar lS! 22.4 (l) was added and stirred for 30 minutes. 200 cc of acetonitrile was added to the reaction solution, stirred for 4 hours, and then incubated overnight. The precipitated crystals were collected by filtration, washed with acetotrile, and dried. Next, the crude crystals were soaked in water. A mixed solution of 100 nQ of ethanol and 10 h of acetonitrile was added, stirred and left overnight. The precipitated crystals were collected by filtration, washed with acetonitrile and ethanol, and dried.
dye was obtained.

The aqueous solution of this dye had a λmax of 627 nm.

The methanol solution of this dye has a λmax of 546 nl! Met.

In the silver halide photographic material of the present invention, the dye represented by the general formula [II] can be incorporated into the silver halide photographic emulsion and used as an irradiation-preventing dye, or it can be used as an irradiation-preventing dye. It can also be incorporated into a photosensitive hydrophilic colloid layer and used as a filter dye or antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or other dyes described below may be used in combination. The dye according to the present invention can be easily incorporated into a silver halide photographic emulsion layer or other hydrophilic colloid layer by a conventional method. Generally, dyes or organic/inorganic alkali salts of dyes are dissolved in aqueous solutions or organic solvents (
For example, alcohols, glycols, cellosolves,
(dimethyl formaldehyde, dibutyl phthalate, tricresyl phosphate, etc.), if necessary emulsified and dispersed, and added to a coating solution for coating to incorporate the dye into the silver halide photographic light-sensitive material. The content of these dyes varies depending on the purpose of use, but
Generally 0.01 to 30 per 112 areas on the photosensitive material
It is applied and used so that it becomes m0.

Next, the auxiliary developer used in the present invention will be explained in detail.

As the auxiliary developer used in the present invention, those known in the art can be used, but preferably those of the following general formula [IV
] to [■] are used.

R';': R,.

(In the formula, R9, R+oz R++ and R12 each represent an alkyl group, and R9 and RIO and/or R
t+ and R+2 may be bonded to each other to form a nitrogen-containing heterocycle with a nitrogen atom. R+3 represents a halogen atom, an alkyl group or an alkoxy group, and nl represents an integer of O to 4. When nl is an integer of 2 to 4, R+s may be the same or different. ) In the general formula [rV],
The alkyl group represented by R9, Rho, R++, and R12 may be linear or branched, and is preferably an alkyl group having 1 to 4 carbon atoms, and this alkyl group includes those having a substituent. For example, hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group, etc.)
, a sulfonamide group (for example, an alkylsulfonamide group such as a methanesulfonamide group, an arylsulfonamide group such as a benzenesulfonamide group), an aryl group (for example, a phenyl group, etc.), and the like. R9, Rho, R
Examples of the alkyl group represented by ++ and R+2 include methyl group, ethyl group, rhopropyl group, i-propyl group, n-butyl group, 5ec-butyl group, hydroxymethyl group, β-hydroxymethyl group, β- Examples include methoxyethyl group and methanesulfonamidoethyl group. R
The nitrogen-containing heterocyclic nucleus formed by 9 and Rho and/or R++ and R+2 may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., such as a pyrrolidine nucleus, a piperidine nucleus, a morpholine nucleus, etc. I can do it.

Examples of the halogen atom represented by R+3 in general formula [IV] include a bromine atom and a chlorine atom, examples of an alkyl group include a methyl group and an ethyl group, and examples of an alkoxy group include a methoxy group. , ethoxy group, etc. The alkyl group and alkoxy group represented by R13 include those having a substituent.

Specific examples of the compound represented by the general formula [IV] used in the present invention are shown below, but the present invention is not limited thereto.

Below margins IV-1 ■-2 IV-3 ■-4 (,
: ni13CH3 IV -71V -8 ■-13 These compounds, with some exceptions, are known (for example, JP-A No. 50-15554, JP-A No. 58-12024).
It is stated in Specification No. 8 etc. ), can be easily synthesized by those skilled in the art. The synthesis of these compounds includes, for example, Bent, Dessloch, Fasset
T. James.

Ruby, 5terner, V 1ttun,
Weissberger; J.

Am, Chem, Sac, 73, 3100
(1951), Bent, Brown, Gle.
smaness, Harnish: Photo,
Sci, Eng, 8. 125 (1964) etc.

General formula [V] (wherein, RH and R+s each represent a hydrogen atom or an alkyl group, and R++ and R+s may combine with each other to form a nitrogen-containing heterocycle. R16 is a halogen atom, an alkyl group, or represents an alkoxy group, n2 is O~
Represents an integer of 4. If n2 is an integer from 2 to 4, R16
may be the same or different. ) In the general formula [V], the alkyl group represented by R++ and R15 may be linear or branched, and is preferably an alkyl group having 1 to 6 carbon atoms, and these alkyl groups may also have a substituent. Substituents include, for example, hydroxy groups, alkoxy groups (such as methoxy groups and ethoxy groups), sulfonamide groups (such as alkylsulfonamide groups such as methanesulfonamide groups, and arylsulfonamide groups such as benzenesulfonamide groups). ) etc. Examples of the alkyl group represented by R14 and R15 include methyl group, ethyl group, butyl group, hexyl group, hydroxymethyl group, β-hydroxyethyl group,
Examples include methoxymethyl group and β-methanesulfonamidoethyl group. The nitrogen-containing heterocyclic nucleus formed by Rn and R15 may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., and examples thereof include a pyrrolidine nucleus, a piperidine nucleus, a piperazine nucleus, a morpholine nucleus, and the like.

Examples of the halogen atoms represented by R+s include bromine atoms and chlorine atoms, examples of alkyl groups include methyl groups and ethyl groups, and examples of alkoxy groups include methoxy groups and ethoxy groups. can be mentioned. The alkyl group and alkoxy group represented by R+s include those having a substituent.

When n2 is 2 to 4, R+s may be the same or different.

Specific examples of the compound represented by the general formula rV used in the present invention are shown below, but the present invention is not limited thereto.

Margin below V-I V-2-3V
-4 V -s V -6
-7y-6 V-11'11/-12 H V-15V-16 V=17 V-18 These compounds are described, for example, in U.S. Pat. 2.776, No. 313,
3.060,225, British Patent No. 928.671
Specification, Berichte der Deutschen Chemitsien Gesellschaft, Vol. 16, p. 724 (3erich
te der Deutschen Chemisch
en Ge5ellschaft) 34 volumes of the same magazine 2
．． 125 pages, Chemissie Berichte 92nd Spring 3.22
3 pages (Chemisch Berichte),
Photographic Science and Engineering Volume 12, Page 41
3science and [:ngineering
) and Journal of the Chemical Society, Vol. 1947, p. 182 (Journal or
It can be synthesized according to the method described in the Chemical Society, etc.

General formula [VI Col I7 (wherein, X represents a hydrogen atom or a hydrolyzable group, R+7 represents an aryl group, R+a, R19, R2
0 and R21 each represent a hydrogen atom, an alkyl group or an aryl group. ) In the general formula [VI], X represents a hydrogen atom or a hydrolyzable group, and the hydrolyzable group represented by X is preferably an acetyl group. X is preferably a hydrogen atom.

Examples of the aryl group represented by Ru in the general formula [Vll include phenyl group and naphthyl group, with phenyl group being preferred. This aryl group includes those having substituents, such as alkyl groups (
Examples include methyl group, ethyl group, propyl group, etc.), halogen atom (chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, etc.), sulfonyl group, amide group (methylamide group, ethylamide group, etc.). be able to.

The alkyl group represented by Rta, R+s, R20, and R21 of the general formula [Vll] preferably includes an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, etc.). This alkyl group includes those having a substituent, and examples of the substituent include a hydroxyl group, an amimu-L acyloxy group, and the like. Further, examples of the aryl group of R18, R1s sR20 and R21 include a phenyl group and a naphthyl group. This aryl group includes those having substituents, such as alkyl groups (methyl group, ethyl group, propyl group, etc.), halogen atoms (chlorine atom, bromine atom, etc.), alkoxy groups (methoxy group, ethoxy group, etc.). groups, etc.) and hydroxyl groups.

Typical specific examples of compounds represented by the general formula [Vll used in the present invention are shown below, but the compounds of the present invention are not limited thereto.

Below margin CH3CH3 VI-19VL-20 VI-21Vl -22 VI-23VI-24 VL-25VI 26 ■-27VI-28 ■-29VI-30 VI-31VI-32 V[-33Vn-34 Vl-35VI-36 Vr- 37VI-3B H3 VI-39Vl-40 Hs VI-43'VL-44 t -45VI-45 t VI-47'VI-48 There are commercially available compounds represented by the general formula [VI]. , U.S. Patent No. 2,688,024, No. 2
．． It can be synthesized according to No. 704.762, JP-A-56-64339, and JP-A-57-211147.

General formula [■] - (In the formula, A and B each represent a secondary amino group bonded to the carbon atom of the mother nucleus through a nitrogen atom, and Y represents a sulfur atom or an oxygen atom.) General formula [■] In , the secondary amino group bonded to the carbon atom of the mother nucleus represented by A and B with a nitrogen atom can contain various aliphatic or aromatic components, and A and 8 may be the same or different from each other. But that's fine.

Specifically, the above A and B are -N H-R22 and -
Each can be expressed as N H-R23, where R
22 and R23 are each an aliphatic group or an aromatic group, and R22 and R23 are preferably electron-donating groups. Specifically, the groups represented by R22 and R23 are:
Examples include alkyl groups, alkenyl groups, aryl groups, etc.
These alkyl groups, alkenyl groups, and aryl groups include those having substituents.

Examples of these substituents include alkoxy groups (eg, methoxy group, ethoxy group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, etc.), and the like. R22 and R23 are, for example, methyl group, ethyl group, propyl group, butyl group, methoxymethyl group, β-methoxyethyl group, β
-Ethoxyethyl group, methylthioethyl group, ethylthiomethyl group, furyl group, phenyl group, methoxyphenyl group, ethoxyphenyl group, methylthiophenyl group, ethylthiophenyl group, and the like.

Specific examples of compounds represented by the general formula [■] used in the present invention are shown below, but the present invention is not limited thereto.

VI-12,5-bis(methylamine)-1゜3.4-
Thiadiazole VI-22-methylamino-5-ethylamino-1,3
,4-thiadiazole W-32,5-bis(ethylamino)-1゜3.4-thiadiazole■-42,5-bis(n-butylamino)-1,3,4
-thiadiazole -52-allylamino-5-methylamino-1,3,
4-Thiadiazole ■-62-(2-ethoxyethylamino)7-5-methylamino-1,3,4- Thiadiazole ■-72,5-bis(phenylamino)-1,3,4-
Thiadiazole -82,5-bis(2-methoxyethylamino)-1
,3,4-thiadiazole■-92-<2-ethoxyethylamino)-5-(2-
methoxyethylamino) -1,3,4-thiadiazole■-102,5-bis(2-ethoxyethylamino)-
1,3,4-thiadiazole■-112=(2-methoxyethylamino)-5-phenylamino-1,3,4-thiadiazole VI-122-(p-methoxyphenylamino)-5-
(2-methoxyethylamino) -1,3,4-thiadiazole -132-(3-methylthiopropylamino)-5-
(2-methoxyethylamino)-1,3,4-thiadiazole VW-142,5-bis(methylamine)-1°3.4
-Oxadiazole■-152,5-bis(ethylamino)-1゜3.4-
Oxadiazole An example of the method for producing the diazole compound represented by the above general formula [VI] is described in JP-A No. 53-61334, P
, C. Guha, Journal of A.
mericanChemical 3ociety,
45, p. 103B (1928), and J.
Our own of Medical Che
mistry, Vol.

15, No. 3, 0.315 (1972), etc.

In order to incorporate the auxiliary developer according to the present invention into a photosensitive material,
Dissolved in water or an organic solvent optionally miscible with water (for example, methanol, ethanol, etc.), or dissolved in an organic solvent (which does not need to be miscible with water) and then dispersed in a hydrophilic colloid. It can be added as a solution or dispersion. The amount of the auxiliary developer according to the present invention added is preferably the total amount contained in the silver halide photographic light-sensitive material.

Per mole of photosensitive silver halide 1. OX'l Q-9
2.0 mol to 2.0 mol, more preferably 1.0X10' to 1
．． It can be used in a range of 5 mol.

The addition may be made at any time from time MY of the silver halide emulsion to the time of coating, but preferably from the end of chemical ripening of the silver halide emulsion to the time of coating. It can be added to any layer of the photosensitive silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer, but generally it is added to the undercoat layer, the lowest layer in contact with the undercoat layer (closest to the support side). layer)
, or to the bottom layer (the emulsion layer closest to the support) of each photosensitive emulsion layer.

In the present invention, by using the above-mentioned auxiliary developer, color development can be promoted and rapid processing becomes possible.

However, an increase in density in the unexposed area (hereinafter referred to as Dmin) occurs, which is thought to be due to an increase in fog in the silver halide emulsion layer which is strongly affected by the auxiliary developer, which has been an obstacle to practical use. It has been found that this increase in [)min can be improved by using a compound represented by the general formula [I] or [II] according to the present invention (hereinafter referred to as "hardening agent of the present invention"). , in this case,
It has been found that this causes a decrease in sensitivity of the red-sensitive emulsion layer during storage over time. This deterioration in the storage stability of the red-sensitive emulsion layer over time is due to
This problem also occurs when the hardener of the present invention is added to a photographic layer other than the above-mentioned red-sensitive emulsion layer.

This is probably because the hardening agent of the present invention has a high diffusivity, so that it diffuses between photographic layers and affects other photographic layers as well. It was completely unexpected that the storage stability of this red-sensitive emulsion over time could be improved by using the compound represented by the general formula [I] according to the present invention.

This is because it is known that the compound represented by the general formula [I[I] is generally used for filters, anti-halation, anti-irradiation, etc. (for example, Japanese Patent Publication No. 51-46607, Kaisho 59-11164
There is a description in No. 0 etc. ), the effect of the present invention, that is, the effect of improving the stability over time of a red-sensitive emulsion layer, was completely unknown.

Next, the silver halide emulsion used in the present invention will be explained.

The silver halide composition of the silver halide emulsion used in the present invention may be silver halide commonly used in light-sensitive materials, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, and silver iodine. Examples include silver oxide, silver chloride iodobromide, and the like. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Preferably, a monodisperse emulsion with a narrow particle size distribution is used.

"Monodisperse silver halide grains" preferably used in this specification mean that the shape of each silver halide grain appears uniform when the emulsion is observed using an electron micrograph;
The particle sizes are uniform and the standard deviation of the particle size distribution is S.
The ratio S/r of S/r to the average particle diameter r is preferably 0.22 or less, more preferably 0.15 or less. Here, the standard deviation S of the particle size distribution is determined according to the following formula.

In addition, the average grain size r referred to here refers to the diameter of spherical silver halide grains, or the projection image of grains of a shape other than cubes or spheres to circular images of the same area. The average diameter when converted (direct), where the individual grain size is ri and the number is ni, 7 is defined by the following formula.

The above particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's [Particle Size Analysis Table JA].

S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122 or chapter 2 of ``Theory of the Photographic Process'' by Mies and Ginimes, 3rd edition, Macmillan Publishing Co., Ltd. (1966). Are listed. The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The relationship between grain size distribution is described in "Empirical relationship between sensitometric distribution and grain size distribution in photographic emulsions," The Photographic Journal, Vol. LXXIX, (1949) 33.
This can be determined by the method described in the article by Trivelli and Smith, pages 0-338.

The average particle diameter of the silver halide grains preferably used in the present invention is not particularly limited in terms of the nature of the invention, but it is preferably 0.1 to 2.0 μm, more preferably 0.1 to 2.0 μm when measured according to the above method. It is in the range of 0.2 to 1.6 μm.

The silver halide grains used in the present invention can be adjusted by controlling ACI, temperature, addition rate, etc., or by selecting various grain formation conditions, and can be adjusted by the usual single shot method or double jet method. can do. Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt is the one-sided mixing method, the simultaneous mixing method,
Any combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which pAg in a solution in which silver halide is produced can be kept constant, ie, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained.

In the present invention, after forming a silver salt with higher solubility than silver bromide as disclosed in U.S. Pat. A conversion method may also be used.

However, it is particularly preferred to use silver chlorobromide emulsions formed without using the conversion methods described above.

Alternatively, two or more silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be present.

In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, please refer to Research Disclosure 17643.
This can be done based on the method described in the issue.

The silver halide grains used in the present invention may consist of uniform layers inside and on the surface, or may consist of different layers.

The silver halide grains used in the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

The silver halide grains used in the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, (1
Any ratio between the 00) plane and the (11i) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion used in the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion used in the present invention is chemically sensitized by a conventional method. That is, a sulfur sensitization method using a sulfur-containing compound that can react with silver ions or activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, and a gold or other noble metal compound. Noble metal sensitization methods can be used alone or in combination.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

The sensitizing dyes may be used alone or in combination of two or more. A supersensitizer, which is a dye that does not itself have a spectral sensitizing effect along with the sensitizing dye, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye, may be included in the emulsion. good.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these. A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus,
Benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus,
These include naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, and quinoline nucleus. These nuclei are
It may also be replaced on the carbon atom.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, deacyridine-2,4-dione nucleus, rhodanine nucleus, thioparturic acid nucleus, and the like can be applied.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat. No. 2,519,001, No. 2
．． No. 912.329, No. 3, No. 656.959, No. 3
．． 672.897, 3,694,217M, 4
, No. 025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 14030/1984,
Examples include those described in No. 52-24844. Also, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 201, No. 2.072,908, No. 2,739,
No. 149, No. 2,945.763, British Patent No. 505
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 1, No. 979, and the like. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include:
For example, U.S. Patent No. 2.269.234, U.S. Pat.
No. 378, No. 2.442.710, No. 2.454.6
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 29, No. 2.776, and No. 280. Furthermore, U.S. Pat. No. 2,213,995, U.S. Pat.
No. 748, No. 2,519,001, West German Patent No. 929.
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publications No. 43-4932, No. 43-4933, No. 43-4936, No. 44-32753, No. 45-
No. 25831, No. 45-26474, No. 46-116
No. 27, No. 46-18107, No. 47-8741,
No. 47-11114, No. 47-25379, No. 47
-37443, 48-28293, 48-38
No. 4H, No. 4B-38407, No. 4B-38408, No. 48-41203, No. 48-41204, No. 4
No. 9-6207, No. 50-40662, No. 53-12
No. 375, No. 54-34535, No. 55-1569, JP-A No. 50-33220, No. 50-33828,
No. 50-38526, No. 51-107127, No. 51-107127, No. 51-107127, No. 51-107127, No.
No. 51-115820, No. 51-135528, No. 51-151527, No. 52-23931, No. 5
No. 2-51932, No. 52-104916, No. 52-
No. 104917, No. 52-109925, No. 52-1
No. 10618, s4-aotig@, 56-257
No. 28, No. 57-1483, No. 58-10753,
No. 58-91445, No. 58-153926, No. 5
No. 9-114533, No. 59-116645, No. 59
-116647, U.S. Patent No. 2.688.545,
2,977.229, 3,397,060, 3.506.443, 3,578,447, 3
．． No. 672.898, No. 3.6791428, No. 3.
No. 769.301, No. 3.814.609, No. 3, 8
No. 37.8132.

Examples of dyes that do not themselves have a spectral sensitizing effect, or compounds that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as aromatic organic acid formaldehyde condensates ( (e.g., those described in U.S. Pat. No. 3,437,510), cadmium salts, azaindene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933);
．． No. 390 and No. 3,635.721). U.S. Pat. No. 3,615.613, U.S. Pat. No. 3,61
No. 5,641, No. 3.617.295, No. 3.635
．． The combinations described in No. 721 are particularly useful.

For the spectral sensitization of the red-sensitive emulsion used in the present invention, sensitizing dyes represented by the following general formula [■], [rX] or [X] are preferably used.

The following is a blank general formula [■] General formula [rX] [In the formula, R24 and R25 each represent an alkyl group or an aryl group, and L+, L2, L3, L4
and L5 represents a methine group. eZ+ and z2 each represent an atom or atomic group necessary to complete the oxazole ring, thiazole ring or selenazole ring. Z
3 represents a group of hydrocarbon atoms necessary to form a 6-membered ring. xe represents an acid anion. ml, "12, n, and 1 do not represent O or 1, respectively. However, when the compound forms an inner salt, 2 is O.] General formula [X co[wherein, Zl is a quinoline ring Z5 is a thiazole ring, a pensive azole ring,
Does not represent an atomic group necessary to constitute a naphthothiazole ring, benzoxazole ring, naphthoxazole ring, benzoselenazole ring, or naphthoselenazole ring. R2
6, R27 and R28 each represent an alkyl group, and Xθ represents an acid anion. m3 and 12 each represent 0 or 1. ] Specific examples of sensitizing dyes represented by the general formulas [■], [IX] and [IX are shown below, but the invention is not limited thereto.

■e Iθ ■e B, θ D-6 B, θ ■θ ■θ D-19 D-20 D・-25 ttd D-32 D-33 1-Ii9 D-45 D-46 The following margins relate to the present invention The general formula [■], [rX] or [X]
The sensitizing dye represented by can be added at any time during the emulsion manufacturing process, but it is preferably added during or after chemical ripening, and more preferably during chemical ripening. The amount added is 10-7 to 10-3 per mole of silver halide.
mol, preferably from 5×10 −6 to 5×10 −mol.

The silver halide emulsion used in the present invention may be used during chemical ripening and/or to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or to maintain stable photographic performance. At the end of the ripening and/or after the end of the chemical ripening and before coating the silver halide emulsion, compounds known in the photographic world as antifoggants or stabilizers other than the compounds of the present invention may be added. I can do it.

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developing agent (for example, a rhophenylenediamine derivative) during color development processing. , dye-forming couplers are used.

The dye-forming couplers are typically selected to form a dye for each emulsion layer that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming dye forming for the blue light sensitive emulsion layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even though these dye-forming couplers are 4-functional, in which 4 silver ions need to be reduced to form one molecule of dye, only 2 silver ions are reduced. Either of the two good motherhoods is fine.

Dye-forming couplers can be used to form development accelerators, bleach accelerators, developing agents, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, and chemical agents by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments such as sensitizers, spectral sensitizers, and desensitizers can be included.

Colored couplers that have a color correction effect on these dye-forming couplers, or DrR that releases a development inhibitor during development and improves image sharpness and image graininess.
A coupler may also be used in combination. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different dye may be used. It may also be one that forms different types of pigments.

Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction in the makuuchi separated by the coupling reaction (timing DIR couplers, and timing DIR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. Although a coupling reaction is carried out with an oxidized product of an aromatic primary amine developer, a colorless coupler that does not form a dye can also be used as Ui with a dye-forming coupler.

As the yellow dye-forming coupler used in the present invention, those represented by the following general formula (A) are preferably used.

General formula (A> In the formula, R29 represents an alkyl group or an aryl group,
R30 represents an aryl group, and X does not represent a hydrogen atom or a group that is eliminated during the color development reaction.

R29 is a linear or branched alkyl group (e.g. butyl group) or aryl group (e.g. phenyl group), preferably an alkyl group (especially [-butyl group), and R3o is an aryl group (preferably phenyl group), and these alkyl groups and aryl groups in R29 and R30 include those with substituents, and R30
The aryl group is preferably substituted with a halogen atom, an alkyl group, or the like. X is the following general formula (B)
Or a group represented by (C) is preferable, and moreover, a group represented by the general formula (
Among B), groups represented by general formula (B') are particularly preferred.

General Formula (B) In the formula, Zl represents a group of nonmetallic atoms that can form a 4- to 7-membered ring.

General formula (C) -O-R31 In the formula, R3+ represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferable.

General formula (B') the law of nature Represents a group of nonmetallic atoms that can be formed.

A preferred yellow coupler according to the present invention in the general formula (A) is represented by the following general formula (A').

General Formula (A') In the formula, R32 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferred.

R33, R34 and R35 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, an alkylsulfonamide group, an acylamide group, It represents a ureido group or an amino group, R33 and R34 are each a hydrogen atom, and R35 is preferably an alkoxycarbonyl group, an acylamido group, or an alkylsulfonamide group. Further, X represents a group having the same meaning as that shown in the above general formula (A), preferably the above general formula (B) or (C
), (B), the general formula (B'
).

Below margin (Y-1) (Y-2) (Y=3) H3 (Y-4) (Y-51 I- (Y-6) (Y-7) ('/- (Y-8) I+II ( Y-9) (Y-10) (Y-11) (Y-12) t (Y-!3) (Y-14) These are, for example, British Patent No. 1,077.874@, Japanese Patent Publication No. 45-40757 JP-A-47-1031, JP-A No. 47-26133, JP-A No. 48-94432, JP-A No. 50-
No. 87650, No. 51-3631, No. 52-115
No. 219, No. 54-99433, No. 54-1333
No. 29, No. 56-30127, U.S. Patent No. 2,875
, No. 057, No. 3.253, No. 924, No. 3,265.
, No. 506, No. 3.408.194, No. 3.551
, No. 155, No. 3,551,156, No. 3,66
No. 4,841, No. 3.725.072, No. 3.730
．． No. 722, No. 3.891.445, No. 3,900,
No. 483, No. 3,929,484, No. 3.933.5
No. 00, No. 3,973,968, No. 3,990,
No. 896, No. 4.012, 259, No. 4,022,
No. 620, No. 4.029.508, No. 4.057.
No. 432, No. 4.106.942, No. 4.133.9
No. 58, No. 4,269,936, No. 4,286,05
No. 3, No. 4,304.845, No. 4,314,023
No. 4,336,327, No. 4.356,258, No. 4,386,155, No. 4.401.752
It is stated in the number etc.

In the silver halide photographic light-sensitive material of the present invention, the magenta dye image-forming coupler has the following general formula [a
] and [aI] can be preferably used.

General formula [a] Ar [wherein Ar represents an aryl group, Rat represents a hydrogen atom or a substituent, and Ra2 represents a substituent. Y is a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent, and W is -NH-1-NHCO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -N HC
represents ON H-, and m is an integer of 1 or 2. ]
In the magenta coupler represented by the general formula [al] below, za represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the Za
The ring formed by may have a substituent.

X represents a hydrogen atom or a substituent which can be eliminated by reaction with an oxidized product of a color developing agent.

5 margins I CH.

t These include, for example, U.S. Patent No. 2.600.788, U.S. Pat.
Same No. 3,127゜269, Same No. 3,311,476, Same No. 3.152.896, Same No. 3,419,391
No. 3,519.429, No. 3,555.31
No. 8, No. 3,684,514, No. 3,888,6
No. 80, No. 3,907,571, No. 3,928,
No. 044, No. 3,930.861, No. 3.930
．． Specifications such as No. 866 and No. 3,933,500, JP-A No. 49-29639, No. 49-111631, No. 49-129538, No. 50-13041, No. 52
-58922, 55-62454, 55-11
No. 8034, No. 56-380434, No. 57-3585
No. 8, Publications No. 60-23855, British Patent No. 1,
No. 247,493, Belgian Patent No. 769,116,
No. 792.525, West German Patent No. 2.156.111
Specifications of each issue, JP-B-46-60479, JP-A-59
-125732, 59-228252, 59
-162548, 59-171956, 60
-33552 and 60-43659, West German Patent No. 1, West German Patent No. 070.030, and US Patent No. 3.725
．． It is described in each specification etc. of No. 067.

As the cyan image forming coupler, the following general formula [E],
[A coupler represented by Fl can be preferably used.

General Formula [E] In the formula, R1 represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2 represents an alkyl group or a phenyl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

zl represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General formula [Fl In the formula, R4F represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). Rs.
t represents alkyl M (eg, methyl group, ethyl group, etc.). R6F is a hydrogen atom, a halogen atom (e.g. fluorine,
(chlorine, bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.).

22F represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

Below, as the margin cyan dye image-forming couplers, phenolic cyan dye image-forming couplers are representative, and are disclosed in U.S. Pat. No. 2,306,410, U.S. Pat. , No. 2.367, 531,
Same No. 2,369.929, Same No. 2.423.73
No. 0, No. 2,474,293, No. 2,476.
No. 008, No. 2,498,466, No. 2,545
, No. 687, No. 2,728,660, No. 2,77
No. 2,162, No. 2,895,826, No. 2,9
No. 76.146, No. 3.002.836, No. 3,
No. 419,390, No. 3,446,622, No. 3
．． 476,563, 3.737,316, 3,758,308, 3.839.044, British Patent No. 478,991, 945,542, 1 , No. 084.480, No. 1.377.233, No. 1,388,024 and No. 1,543°04
Each specification of No. 0, as well as JP-A Nos. 47-37425, 50-10135, 50-25228, and 50
-112038, 50-11'7422, 50
-130441, 5l-sss1@, 51-37
No. 647, No. 51-52828, No. 51-10884
No. 1, No. 53-109630, No. 54-48237
No. 54-66129, No. 54-131931,
It is described in the following publications: No. 55-32071, No. 59-146050, No. 60-117249, and No. 59-31953.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may be included.

The photosensitive material of the present invention can be provided with a single filter layer, and auxiliary layers such as an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, increasing the ease of writing, preventing mutual scratching of the light-sensitive materials, etc. .

A lubricant can be added to reduce the sliding friction of the photosensitive material of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or in the emulsion layer and/or the antistatic layer.
Alternatively, it may be used in a protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated on the support.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention includes improved coating properties, antistatic properties, improved slipperiness,
Various surfactants are used for the purpose of emulsification dispersion, prevention of adhesion, and improvement of photographic properties (such as development acceleration, contrast enhancement, sensitization, etc.).

The light-sensitive material of the present invention has a photographic emulsion layer, and other layers include a flexible reflective support such as baryta paper, paper laminated with α-olephne polymer, etc., synthetic paper, cellulose acetate, cellulose nitrate, polybrene, polychloride, etc. Films made of semi-synthetic or synthetic polymers such as vinyl, boreethylene terephthalate, polycarbonate, polyamide, glass,
Can be applied to rigid bodies such as metal and ceramics.

The photosensitive material of the present invention can be prepared directly or (
one or more subbing layers (to improve adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, frictional properties and/or other properties of the support surface); It may also be applied through.

When coating the photosensitive material of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

The exposure time is of course 1 millisecond to 1 second, which is normally used with a camera, but it is also possible to use an exposure shorter than 1 microsecond, for example, an exposure of 100 microseconds to 1 microsecond using a cathode ray tube or xenon arc lamp. Exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The photosensitive material of the present invention can form an image by performing color development as known in the art.

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones that are widely used in various color photographic processes.

These phenomenon agents include p-phenylenediamine derivatives. Since these compounds are more stable than the free state, they are generally in salt form, such as the hydrochloride or 1ii! Used in the form of lysate. In addition, these compounds are generally used in color developer 1.
The color developer 12 is preferably used in a concentration of about 0.1 g to about 30 g per color developer, preferably about 1 g to about 150 g per color developer.

Particularly useful primary aromatic amine coloring agents include N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamine)-toluene, N-ethyl-N-β-methanesulfonamidoethyl 3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned aromatic primary amine color developer, the color developer used in the process of the present invention further contains various components normally added to color developers, such as sodium hydroxide and sodium carbonate. , an alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali synthetic bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickening agent. The pH value of this color developer is usually 7 or higher, most commonly about 10 to
It is about 13.

The auxiliary developer of the present invention can be used by being added to a color developing solution, if necessary.

When added to color developer, the addition M is color developer 1
1 to 500 mg per serving, more preferably 10 to 3 oo
mg range.

The auxiliary developer used in the present invention can be added to the color developer by dissolving it in one or a mixture of two or more suitable solvents, such as methanol, ethanol, isopropanol, acetone, dimethylformamide, etc. , may be added to the color developing solution.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complex salts of talic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[I] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt Salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used contains the metal complex salts of various acids as mentioned above as a bleaching agent, and can also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, fl of borate, oxalate, acetate, carbonate, phosphate etc.
Those known to be added to ordinary bleaching solutions, such as H buffering agents, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, It may contain one or more pH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, thiosulfate, thiocyanine, etc. are added to the bleach-fix solution (bath). Salts or sulfites or the like may be included, or the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

[Examples] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

[Example-1] A silver halide photographic light-sensitive material having the structure shown in Table 1 was prepared on a paper support coated with polyethylene on both sides by a conventional method, and was designated as Comparative Sample-1. However, the red-sensitive silver chlorobromide emulsion in the fifth layer was spectrally sensitized using exemplary sensitizing dye D-2. Further, in the fifth layer, DR-1 was used as a comparative dye for the dye of the present invention.

Next, Comparative Samples-2 to 9 were prepared in the same manner as Comparative Sample-1 except that the auxiliary developer according to the present invention was added to the second layer and the hardener and dye were changed as shown in Table-2. Samples 1o to 13 of the present invention were prepared.

Table 1 Ultraviolet absorption side (UV-1) (CH-1) C(CH20CH2SO2CH=CH2)4(DR-1
) Samples 1 to 13 were exposed to white light using a photosensitive needle (KS-7 model manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following treatments.

Margin standard processing steps below (processing temperature and processing time) [I] Color development 38°C 1 minute [2 bleach-fixing 33°C 1 minute 30 seconds [3] Washing process 25-30°C 3 minutes - [4] Drying 75 ～80℃ for about 2 minutes Color development liquid [
△] Composition Benzyl alcohol 5nj2 Ethylene glycol 151g
J'J Ram 2. OQ Potassium bromide 0.7g Sodium chloride 0.29 Potassium carbonate
50 Q Human O-xylamine sulfate 3.0g polyphosphoric acid (TPPS)
2.5!13-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfur ml 8g optical brightener (4,4'-diaminostilbenesulfone 111m conductor) 1.0
g Potassium hydroxide 2.0Q water was added to bring the total amount to 1, and the total amount was adjusted to I) 811.0.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate eo g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100-n
, N ammonium sulfite (40% solution) 27.5
Adjust the pH to 7.1 with iN potassium carbonate or glacial acetic acid, and add water to bring the total volume to 12.

The reflection density of the obtained sample was measured using a PDA-65 model i1 degree meter (manufactured by Konishiroku Photo Industry ■), and the maximum density □
mtn and sensitivity (the reciprocal of the exposure range required to give a density of Dmin + 0.5) were determined. In addition, the storage stability over time was evaluated by the change in sensitivity (%) using the following method. The results are shown in Table-2.

Evaluation of storage stability over time> Storage stability over time was evaluated by the change in sensitivity before storage and after being left at 40° C. and 40% (relative humidity), and was expressed as a rate of change in sensitivity expressed by the following formula. The sensitivity was determined by performing the light wedge exposure described above, then performing the development treatment described above, and measuring the density.

From the margin table-2 below, sample-2 using the auxiliary developer according to the present invention
In samples 1 to 13, color development is promoted, but samples 2 to 5 using the auxiliary developer according to the present invention and not using the hardener of the present invention [) w
An increase in in is seen.

(In the case of D win, ±0.01 is within the experimental error range, and there is no problem in practice, but when it comes to + O, OS, 'WX' can be clearly recognized visually, and it is at a level that poses a quality problem.) ) The above increase in D 1n is noticeable in the blue density, so it seems that the addition of the auxiliary developer induced fog in the first layer silver halide emulsion. On the other hand, in samples 6 to 9 in which the hardening agent of the present invention was added to the seventh layer, the D min of the first layer decreased and the stability over time of the fifth layer deteriorated. This is considered to be because the hardening agent of the present invention diffused into the fifth layer and the first layer and exerted its effects. In contrast to Samples 6 to 9 above, Samples 10 to 13 in which the dyes of the present invention were used in combination maintained rapid processability and a low D min level, while also maintaining stability over time of the fifth layer (red-sensitive emulsion layer). The results are improved and the effects of the present invention can be confirmed.

[Example 2] The auxiliary developer ■-16 according to the present invention was added to the first layer in an amount of 2 x 10-2 mol 1 mol Ag x), and the hardener and dye shown in Table 3 were used. , the dye additive layer was added to the fourth layer and the sixth layer (the amount added was 52<1/l for both the fourth layer and the sixth layer).
Samples 14 to 23 were prepared in the same manner as in Table 1 in Example 1, except for the following.

The above samples 14 to 23 were evaluated for Dmin and storage stability over time in the same manner as in Example 1. The results are shown in Table-3.

Table 3 shows that even if the types of hardeners and dyes according to the present invention and the photographic layer to which they are added are changed, the V as defined in the present invention is still maintained. It can be seen that the effects of the present invention can be obtained as in Example-1 if the values are within the range.

Below margin (CH-2) C285C(CH2S O□CH=CH2)3(DR-
2) CH2, CH2 and below margins [Example 3] 3- in the color developer [A] used in Example 1
Instead of methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate, 3
-Methyl-4-amino-N-ethyl-N-hydroxyethyl-aniline sulfate, 3-methyl-4-amino-N-
Color developing solutions [B] and [C] were prepared with the same composition except that ethyl-N-(2-methoxyethyl)-aniline p-tolune sulfonate was used in equimolar amounts.

Example [1] Except for using the above color developer [8] and [C].
When tested in the same manner as in Example [I], almost the same results as in Example [I] were obtained.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (informal) % formula % 2. Name of the invention Silver halide photographic light-sensitive material 3. Person making the amendment' Relationship to the case Patent applicant address 1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Chome 26-2 Name (127)
Benko Konishiroku Photo Industry Co., Ltd. Representative Director
Keio 4, Agent 102 Address: 1-1 Kudankita 4-chome, Chiyoda-ku, Tokyo (Delivery date) April 22, 1986 6. Engraving of the entire text of the specification subject to amendment (no change in content) 7. Amendment contents of

Claims (1)

[Scope of Claims] A halogenated support having photographic constituent layers consisting of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a non-light-sensitive layer. In the silver photographic light-sensitive material, at least one of the photographic constituent layers contains an auxiliary developer, and at least the photographic constituent layer containing the auxiliary developer has the following general formula [I
] and/or [II], and in combination with the red-sensitive silver halide emulsion layer, a compound represented by the following general formula [III] forms at least one of the photographic constituent layers. A photographic material containing silver halide in a single layer. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, -OM group (M is a monovalent metal atom), -NR 'R''(R' and R'' are hydrogen atoms, alkyl groups, and aryl groups, respectively) or -NHCO
R''' group (R''' is a hydrogen atom, an alkyl group, or an aryl group), and R_2 represents a group having the same meaning as R_1. However, R_1 and R_2 do not become chlorine atoms at the same time. ] General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc. represent Q and Q' are each a linking group selected from -O-, -S-, -NH-, L
represents an alkylene group or an arylene group. l and m each represent 0 or 1. ] General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_5 and R_6 are -CN or -, respectively]
CFR'R'' and R' and R'' each represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms. R_7 and R_8 each represent an aliphatic group, an aromatic group or a heterocyclic group. ]